Film-forming composition, film formed thereby, and method for manufacturing organic semiconductor element using same

ABSTRACT

A film-forming composition according to the present invention include fluororesin having a repeating unit of the general formula (1); and a fluorine-containing solvent. 
                         
In the general formula (1), R 1  each independently represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; and R 2  each independently represents C 1 -C 15  straight, C 3 -C 15  branched or C 3 -C 15 cyclic fluorine-containing hydrocarbon gr which any hydrogen atom may be replaced by a fluorine atom with the proviso that the repeating unit contains at least one fluorine atom. This film-forming composition is suitably usable for the manufacturing of an organic semiconductor element because the composition can form a film on an organic semiconductor film; and the formed film has resistance to an etching solvent during the fine pattern processing of the organic semiconductor film by photolithography etc.

FIELD OF THE INVENTION

The present invention relates to a film-forming composition for forminga film on an organic semiconductor film. The present invention alsorelates to a film formed from the film-forming composition and a methodfor manufacturing an organic semiconductor element using such a film.

BACKGROUND ART

Organic semiconductor materials are organic substances having theproperties of semiconductors. There are known various organicsemiconductor materials and organic charge-transfer materials,including: organic low-molecular compounds such as pentacene,anthracene, tetracene and phthalocyanine; polyacetylene-based conductivepolymers; polyphenylene-based conductive polymers such aspolyparaphenylene and derivatives thereof, polyphenylene vinylene andderivatives thereof and the like; heterocyclic conductive polymers suchas polypyrrole and derivatives thereof, polythiophene and derivativesthereof, polyfuran and derivatives thereof and the like; and ionicconductive polymers such as polyaniline and derivatives thereof. Inparticular, some organic semiconductor materials e.g. organiclow-molecular semiconductor and polythiophene can be applied as films toorganic substrates e.g. organic polymer substrates by wet processes. Itis feasible to manufacture flexible organic electrochromic displays byprocessing such organic semiconductor films into semiconductor circuitson the organic substrate materials.

The manufacturing of semiconductor elements involves fine processing(sometimes referred to as “pattern processing”) of semiconductor filmsinto desired semiconductor circuits. At this time, coating films areapplied to protect the semiconductor films during the fine processing orto protect the circuit patterns after the fine processing.

It is often the case to process the semiconductor film into a circuitpattern by means of a photolithography process. The photolithographyprocess is a technique to apply a photosensitive material (called“resist”) to a substrate, exposing the resist-coated substrate through aphotomask or reticle and form a pattern of exposed and unexposed resistregions. The semiconductor film is processed into a circuit pattern byforming a resist pattern through exposure and development of the resistfilm, and then, dry-etching or wet-etching the semiconductor film.

In the manufacturing of the organic semiconductor element, it isconceivable to form a pattern on the organic semiconductor film by aprint process such as relief printing, intaglio printing, planographicprinting or screen printing or an imprint process in place of thephotolithography process and etch the organic semiconductor film throughthe pattern. Herein, the imprint process is a technique to apply acoating film to a substrate, allowing a die having a fine pattern ofprojections and depressions to be pressed against the coating film andthereby transfer the pattern of the die to the coating film.

During the pattern processing of the organic semiconductor film by wetetching, a coating film is applied to the organic semiconductor filmsuch that the organic semiconductor film can be protected from anetchant solvent. It is required that a film-forming composition forforming such a protection film satisfies two important conditions. Thefirst condition is that the film-forming composition is soluble in asolvent that does not cause dissolution or swelling of the organicsemiconductor film and thus can be applied to the organic semiconductorfilm by a wet process. The second condition is that, during the patternprocessing of the organic semiconductor film, the wet-coating film canprotect the organic semiconductor film from etching. However, it hasbeen difficult to obtain film-forming composition satisfying both ofthese two conditions.

There are two etching processes: one is a dry etching process usingplasma irradiation in a vacuum device; and the other is a wet etchingprocess using a solvent as an etchant. The wet etching process isconvenient for etching of the organic semiconductor film because theorganic semiconductor film is soluble in the etchant. In general, theorganic semiconductor film has an aromatic ring group or heterocyclicgroup in its structure and can readily be dissolved in an aromaticsolvent such as benzene, toluene and xylene.

For example, Patent Documents 1 and 2 disclose film-forming compositionsand films formed therefrom such that the films have high etchantresistance and remain unaffected by etchants during the etching oforganic semiconductor films into semiconductor circuit patterns.

More specifically, Patent Document 1 discloses a method formanufacturing an organic semiconductor element with stable electricalcharacteristics and an organic semiconductor element manufacturedthereby, wherein, during the manufacturing of the organic semiconductorelement, a coating film is formed on an organic semiconductor film bythe application of a liquid film-forming composition containing at leastone organic solvent selected from propylene carbonate, acetonitrile anddimethyl sulfoxide and an organic compound soluble in the organicsolvent.

Patent Document 2 discloses a photosensitive resin composition forforming a coating film with high photoreactivity, good patterningproperty, high hydrophobicity and good dielectric characteristics, athin film formed therefrom and a pattern formation method thereof,wherein the photosensitive resin composition contains a solvent such asalcohol, hydrocarbon, halogenated hydrocarbon, ether, ester, ketone,cellosolve, carbitol, glycol ether ester, amide, sulfoxide or nitrile.

However, it can hardly be said that the organic solvent of thefilm-forming composition of Patent Document 1 and the solvent of thephotosensitive resin composition of Patent Document 2 do not affectorganic semiconductor films. There has thus been a demand for afilm-forming composition and a film formed therefrom that can be appliedto an organic semiconductor film, without affecting the organicsemiconductor film, and can be patterned by e.g. a photolithographyprocess or imprint process.

Furthermore, Patent Document 3 discloses a positive resist compositionfor use by exposure to vacuum ultraviolet laser radiation, comprising:an acrylic resin capable of changing its solubility in an alkalineaqueous solution by the action of an acid; and an acid generator,wherein the acrylic resin contains a polymer having an acrylic ester ormethacrylic ester moiety with a fluorine-containing ester group.

Patent Document 4 discloses a positive resist composition for use byexposure to vacuum ultraviolet laser radiation of 1 nm to 190 nmwavelength, comprising: an acrylic resin capable of changing itssolubility in an alkaline aqueous solution by the action of an acid; andan acid generator, wherein the acrylic resin has a unit obtained bypolymerization of fluoroalkyl methacrylate.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: Japanese Laid-Open Patent Publication No. 2012-74616

Patent Document 2: Japanese Laid-Open Patent Publication No. 2011-180269

Patent Document 3: Japanese Laid-Open Patent Publication No. 2001-154362

Patent Document 3: Japanese Laid-Open Patent Publication No. 2005-99856

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

It is accordingly an object of the present invention to provide a filmthat can be applied to an organic semiconductor film, without affectingthe organic semiconductor film, can be patterned by a photolithographyprocess or imprint process etc. and does not become affected by anetchant during the wet etching of the organic semiconductor film into asemiconductor circuit pattern. It is also an object of the presentinvention to provide a film-forming composition for forming such a filmand a method for manufacturing an organic semiconductor element usingsuch a film.

Means for Solving the Problems

As a result of extensive researches, the present inventors have foundthat a fluorine-containing solvent such as fluorine-containinghydrocarbon or fluorine-containing ether, when applied by a wet process,causes less influence such as dissolution or swelling of an organicsemiconductor film as compared to the solvents of Patent Documents 1 and2. Based on this finding, the present inventors have further searchedfor a fluororesin that is soluble in a fluorine-containing solvent suchas fluorine-containing hydrocarbon or fluorine-containing ether andunaffected by an etchant during the etching of an organic semiconductorfilm into a circuit pattern, and then, have resultantly found out afluororesin for forming a fluororesin film on an organic semiconductorfilm and a fluorine-containing solvent for dissolving such a fluororesinand obtained a film-forming composition containing the fluororesin andthe fluorine-containing solvent. The present invention has beenaccomplished by these efforts.

The present invention provides a film-forming composition for forming afluororesin film on an organic semiconductor film, comprising: afluorine-containing solvent that causes significantly less dissolutionor swelling of organic semiconductor film; and a specific fluororesinsoluble in the fluorine-containing solvent and having good etchantresistance. The present invention also provides a film formed from sucha film-forming composition and a method for manufacturing an organicsemiconductor element using such a film. The film-forming composition ofthe present invention can be applied by a wet process to an organicsemiconductor film on an inorganic substrate or organic polymersubstrate so as to form the fluororesin film on the organicsemiconductor film without affecting the organic semiconductor film andthe organic polymer substrate. The fluororesin film can be patterned bye.g. a lithography process, print process or imprint process. As thefluororesin film is difficult to dissolve in a hydrocarbon or aromaticsolvent such as benzene, toluene or xylene used as an etchant foretching of the organic semiconductor film, the organic semiconductorfilm can be etched through the pattern of the fluororesin film. Thefluororesin film is thus suitably applicable to the manufacturing of theorganic semiconductor element.

Namely, the present invention includes the following aspects 1 to 23.

[Inventive Aspect 1]

A film-forming composition for forming a fluororesin film on an organicsemiconductor film, comprising:

a fluororesin having a repeating unit of the general formula (1)

where R¹ each independently represents a hydrogen atom, a fluorine atom,a methyl group or a trifluoromethyl group; and R² each independentlyrepresents a C₁-C₁₅ straight, C₃-C₁₅ branched or C₃-C₁₅ cyclicfluorine-containing hydrocarbon group in which any hydrogen atom may bereplaced by a fluorine atom with the proviso that the repeating unitcontains at least one fluorine atom; and

a fluorine-containing solvent.

[Inventive Aspect 2]

The film-forming composition according to Inventive Aspect 1, whereinthe fluorine-containing solvent includes either a fluorine-containinghydrocarbon or a fluorine-containing ether.

[Inventive Aspect 3]

The film-forming composition according to Inventive Aspect 2, whereinthe fluorine-containing solvent includes, as the fluorine-containinghydrocarbon, a C₄-C₈ straight, branched or cyclic hydrocarbon in whichat least one hydrogen atom is replaced by a fluorine atom.

[Inventive Aspect 4]

The film-forming composition according to Inventive Aspect 2, whereinthe fluorine-containing solvent includes, as the fluorine-containingether, a fluorine-containing ether of the general formula (2)R³—O—R⁴  (2)where R³ and R⁴ each independently represent a C₁-C₁₅ straight, C₃-C₁₅branched or C₃-C₁₅ cyclic hydrocarbon group; at least one hydrogen atomof the ether is replaced by a fluorine atom.

[Inventive Aspect 5]

The film-forming composition according to any one of Inventive Aspects 1to 4, wherein the fluorine-containing solvent further includes afluorine-containing alcohol of the general formula (3)R⁵—OH  (3)where R⁵ represents a C₁-C₁₅ straight, C₃-C₁₅ branched or C₃-C₁₅ cyclichydrocarbon group in which at least one hydrogen atom is replaced by afluorine atom.

[Inventive Aspect 6]

The film-forming composition according to any one of Inventive Aspects 1to 5, wherein the fluororesin has a fluorine content of 30 to 65 mass %.

[Inventive Aspect 7]

The film-forming composition according to any one of Inventive Aspects 1to 6, wherein the fluorine-containing solvent has a fluorine content of50 to 70 mass %.

[Inventive Aspect 8]

A fluororesin film formed by applying the film-forming compositionaccording to any one of Inventive Aspects 1 to 7 onto an organicsemiconductor film.

[Inventive Aspect 9]

A manufacturing method of an organic semiconductor element, comprising:

applying the film-forming composition according to any one of InventiveAspects 1 to 7 onto an organic semiconductor film, thereby forming afluororesin film;

patterning the fluororesin film; and

etching the organic semiconductor film into a pattern.

[Inventive Aspect 10]

The manufacturing method according to Inventive Aspect 9, wherein thepatterning of the fluororesin film is performed by a photolithographyprocess.

[Inventive Aspect 11]

The manufacturing method according to Inventive Aspect 9, wherein thepatterning of the fluororesin film is performed by a print process.

[Inventive Aspect 12]

The manufacturing method according to Inventive Aspect 9, wherein thepatterning of the fluororesin film is performed by an imprint process.

[Inventive Aspect 13]

The manufacturing method according to any one of Inventive Aspects 9 to12, wherein the etching of the organic semiconductor film is performedby a wet etching process using an aromatic solvent.

[Inventive Aspect 14]

The manufacturing method according to Inventive Aspect 13, wherein thearomatic solvent is benzene, toluene or xylene.

[Inventive Aspect 15]

The manufacturing method according to any one of Inventive Aspects 9 to14, further comprising: removing the fluororesin film.

[Inventive Aspect 16]

The manufacturing method according to Inventive Aspect 15, wherein theremoving of the fluororesin film is performed by dissolving thefluororesin film in a fluorine-containing solvent.

[Inventive Aspect 17]

The manufacturing method according to Inventive Aspect 16, wherein thefluorine-containing solvent includes either a fluorine-containinghydrocarbon or a fluorine-containing ether.

[Inventive Aspect 18]

The manufacturing method according to Inventive Aspect 17, wherein thefluorine-containing solvent includes, as the fluorine-containinghydrocarbon, a C₄-C₈ straight, branched or cyclic hydrocarbon in whichat least one hydrogen atom is replaced by a fluorine atom.

[Inventive Aspect 19]

The manufacturing method according to Inventive Aspect 17, wherein thefluorine-containing solvent includes, as the fluorine-containing ether,a fluorine-containing ether of the general formula (2)R³—O—R⁴  (2)where R³ and R⁴ each independently represents a C₁-C₁₅ straight, C₃-C₁₅branched or C₃-C₁₅ cyclic hydrocarbon group; and at least one hydrogenatom of the ether is replaced by a fluorine atom.

[Inventive Aspect 20]

The manufacturing method according to any one of Inventive Aspects 16 to19, wherein the fluorine-containing solvent further includes afluorine-containing alcohol of the general formula (3)R⁵—OH  (3)where R⁵ represents a C₁-C₁₅ straight, C₃-C₁₅ branched or C₃-C₁₅ cyclichydrocarbon group in which at least one hydrogen atom is replaced by afluorine atom.

[Inventive Aspect 21]

An organic semiconductor element manufactured by the manufacturingmethod according to any one of Inventive Aspects 9 to 20.

[Inventive Aspect 22]

An organic electroluminescence display comprising the organicsemiconductor element according to Inventive Aspect 21.

[Inventive Aspect 23]

A liquid crystal display comprising the organic semiconductor elementaccording to Inventive Aspect 21.

The film-forming composition of the present invention, when applied toan organic semiconductor film, does not affect the organic semiconductorfilm by dissolution or swelling. The fluororesin film can be thus formedfrom the film-forming composition on the organic semiconductor film by awet process. Further, the fluororesin film can be patterned by aphotolithography process, print process or imprint process and remainunaffected by the etchant such as hydrocarbon solvent or aromaticsolvent during the wet etching of the organic semiconductor film.

When the film-forming composition of the present invention is applied toan organic semiconductor film, the fluorine-containing solvent of thefilm-forming composition does not cause dissolution or swelling of theorganic semiconductor film. The fluororesin film can be thus formed fromthe film-forming composition on the organic material by a wet process.Further, the fluororesin film can be patterned by a photolithographyprocess, print process or imprint process and does not become affectedby the etchant such as hydrocarbon solvent or aromatic solvent duringthe wet etching of the organic semiconductor film.

In this way, it is possible by using the film-forming composition of thepresent invention to form a semiconductor circuit pattern by fineprocessing of the organic semiconductor film on the substrate. Thefilm-forming composition of the present invention is therefore suitablyusable for the manufacturing of the organic semiconductor element.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-1E are a schematic view of a manufacturing method of an organicsemiconductor element using a film-forming composition, where FIG. 1Ashows a workpiece in which an organic semiconductor film is formed on asubstrate; FIG. 1B shows the workpiece after the formation of afluororesin film on the organic semiconductor film; FIG. 1C shows theworkpiece after the patterning of the fluororesin film; FIG. 1D showsthe workpiece after the wet etching of the organic semiconductor film;and FIG. 1E shows the workpiece after the removal of the fluorine film.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Hereinafter, a film-forming composition of the present invention and amanufacturing method of an organic semiconductor element using thefilm-forming composition will be described below.

The film-forming composition of the present invention includes not onlya fluororesin for formation of a film but also a fluorine-containingsolvent for application as a solution.

1. Fluororesin

In the film-forming composition of the present invention, thefluororesin has a repeating unit of the general formula (1).

In the general formula (1), R¹ each independently represents a hydrogenatom, a fluorine atom, a methyl group or a trifluoromethyl group; and R²each independently represents a C₁-C₁₅ straight, C₃-C₁₅ branched orC₃-C₁₅ cyclic hydrocarbon group in which any hydrogen atom may bereplaced by a fluorine with the proviso that the repeating unit containsat least one fluorine atom.

As the repeating unit (1) contains a fluorine atom, the fluororesin hascompatibility with the fluorine-containing solvent. The coating film ofthe fluororesin has high flexibility and can attain flatness withoutcracking as the repeating unit (1) has a polar ester bond group adjacentto the main chain. Further, the fluororesin has not only high solubilityin the fluorine-containing solvent but also high resistance to anetching solvent as the repeating unit has a fluorinated hydrocarbongroup on the side chain.

For ease of monomer synthesis, R² is preferably a C₂-C₁₄ straight orC₃-C₆ branched hydrocarbon group in which at least one hydrogen atom isreplaced by a fluorine atom.

Specific examples of the straight hydrocarbon group as R² are methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and C₁₀-C₁₄straight hydrocarbon groups. In R², any of hydrogen atoms on carbonatoms, except that directly bonded to oxygen, may be replaced by afluorine atom.

As the straight hydrocarbon group R², particularly preferred is a groupof the general formula (4).

CH₂

_(n)

CF₂

_(m)X  (4)In the general formula (4), X represents a hydrogen atom or a fluorineatom; n is an integer of 1 to 4; and m is an integer of 1 to 14.

For ease of monomer synthesis, n is preferably an integer of 1 to 2 forease of monomer synthesis.

Specific examples of the branched hydrocarbon group as R² are1,1,1,3,3,3-hexafluoroisopropyl,1-(trifluoromethyl)-2,2,3,3,3-pentafluoropropyl,1,1-bis(trifluoromethyl)-2,2,2-trifluoroethyl and1,1-bis(trifluoromethyl)ethyl.

In the film-forming composition of the present invention, thefluororesin has one kind, or two or more kinds, of the repeating unit ofthe general formula (1). The fluororesin may has any repeating unitother than the repeating unit of the general formula (1).

The fluororesin is obtained by e.g. polymerization of an acrylic acidester derivative of the general formula (5) as a monomer.

In the general formula (5), R¹ and R² have the same definitions as thosein the general formula (1).

There is no particular limitation on the acrylic acid ester derivativeas the monomer as long as it is represented by the general formula (5).

In the case where R² is a branched hydrocarbon group in the generalformula (5), there can preferably be used an acrylate, methacrylate,α-fluoromethacrylate or α-trifluoromethylacrylate derived from1,1,1,3,3,3-hexafluoropropane-2-ol (CF₃CH(OH)CF₃),1,1,1,3,3,4,4,4-octafluorobutane-2-ol (CF₃CH(OH)CF₂CF₃),2-trifluoromethyl-1,1,1,3,3,3-hexafluoropropane-2-ol ((CF₃)₂COH) or2-trifluoromethyl-1,1,1-trifluoropropane-2-ol ((CF₃)₂(CH₃)COH) asindicated below.

In the case where R² is a straight hydrocarbon group in the generalformula (5), there can be used a monomer compound of the general formula(6).

In the general formula (6), R⁶ represents a hydrogen atom, a fluorineatom, a methyl group or a trifluoromethyl group; R⁷ represents ahydrogen atom or a fluorine atom; n represents an integer of 1 to 4; andm represents an integer of 1 to 14.

For ease of monomer synthesis, n is preferably an integer of 1 to 3; andm is an integer of 1 to 14 in the general formula (6).

Further, R⁶ is preferably a hydrogen atom or a methyl group for ease ofmonomer synthesis in the general formula (6).

It is preferable that the fluororesin, which is obtained bypolymerization of the above monomer, has a fluorine content of 30 to 65mass %, more preferably 40 to 55 mass %, based on the total mass of thefluororesin. The fluororesin is readily soluble in thefluorine-containing solvent when the fluorine content of the fluororesinis within the above specific range.

Furthermore, the fluororesin preferably has a weight-average molecularweight of 2,000 to 200,000, more preferably 3,000 to 15,000. When themolecular weight of the fluororesin is smaller than 2,000, thefluororesin may not have sufficient resistance to etching solvent. Whenthe molecular weight of the fluororesin is greater than 200,000, it maybecome difficult to form the fluororesin film due to insufficientsolubility of the fluororesin in the fluorine-containing solvent.

Preferred examples of the monomer compound of the general formula (6)are those having the following combinations of R⁶, R⁷, n and m. Amongothers, particularly preferred are those of No. 2-9, 11, 12, 15, 16 and19 in TABLE 1, No. 40, 43, 44, 47-55, 57 and 58 in TABLE 2 and No. 85,88, 91, 92, 94-103 and 105 in TABLE 3.

TABLE 1 Examples of Repeating Unit No. n m R⁶ R⁷ 1 1 1 F H 2 1 1 CF₃ H 31 1 CH₃ F 4 1 1 H F 5 1 1 F F 6 1 1 CF₃ F 7 1 2 CH₃ H 8 1 2 H H 9 1 2 FH 10 1 2 CF₃ H 11 1 2 CH₃ F 12 1 2 H F 13 1 2 F F 14 1 2 CF₃ F 15 1 4CH₃ H 16 1 4 H H 17 1 4 F H 18 1 4 CF₃ H 19 1 4 CH₃ F 20 1 4 H F 21 1 4F F 22 1 4 CF₃ F 23 1 6 CH₃ H 24 1 6 H H 25 1 6 F H 26 1 6 CF₃ H 27 1 6CH₃ F 28 1 6 H F 29 1 6 F F 30 1 6 CF₃ F 31 1 8 CH₃ H 32 1 8 H H 33 1 8F H 34 1 8 CH₃ F 35 1 8 H F 36 1 10 CH₃ H 37 1 10 H H 38 1 10 CH₃ F

TABLE 2 No. n m R⁶ R⁷ 39 2 1 F H 40 2 1 CF₃ H 41 2 1 CH₃ F 42 2 1 H F 432 1 F F 44 2 1 CF₃ F 45 2 2 CH₃ H 46 2 2 H H 47 2 2 F H 48 2 2 CF₃ H 492 2 CH₃ F 50 2 2 H F 51 2 2 F F 52 2 2 CF₃ F 53 2 4 CH₃ H 54 2 4 H H 552 4 F H 56 2 4 CF₃ H 57 2 4 CH₃ F 58 2 4 H F 59 2 4 F F 60 2 4 CF₃ F 612 6 CH₃ H 62 2 6 H H 63 2 6 F H 64 2 6 CF₃ H 65 2 6 CH₃ F 66 2 6 H F 672 6 F F 68 2 6 CF₃ F 69 2 8 CH₃ H 70 2 8 H H 71 2 8 F H 72 2 8 CF₃ H 732 8 CH₃ F 74 2 8 H F 75 2 8 F F 76 2 10 CF₃ F 77 2 10 CH₃ H 78 2 10 H H79 2 10 F H 80 2 10 CH₃ F 81 2 12 H F 82 2 12 CH₃ H 83 2 12 CH₃ F

TABLE 3 No. n m R⁶ R⁷ 84 3 1 F H 85 3 1 CF₃ H 86 3 1 H F 87 3 1 F F 88 31 CF₃ F 89 3 2 CH₃ H 90 3 2 H H 91 3 2 F H 92 3 2 CF₃ H 93 3 2 CH₃ F 943 2 H F 95 3 2 F F 96 3 2 CF₃ F 97 3 4 CH₃ H 98 3 4 H H 99 3 4 F H 100 34 CF₃ H 101 3 4 CH₃ F 102 3 4 H F 103 3 4 F F 104 3 4 CF₃ F 105 3 6 CH₃H 106 3 6 H H 107 3 6 F H 108 3 6 CF₃ H 109 3 6 CH₃ F 110 3 6 H F 111 36 F F 112 3 6 CF₃ F 113 3 8 CH₃ H 114 3 8 H H 115 3 8 F H 116 3 8 CF₃ H117 3 8 CH₃ F 118 3 8 H F 119 3 8 F F 120 3 8 CF₃ F 121 3 10 CH₃ H 122 310 H H 123 3 10 F H 124 3 10 CF₃ H 125 3 10 CH₃ F 126 3 10 H F 127 3 10F F 128 3 12 CH₃ H 129 3 12 H H 130 3 12 F H 131 3 12 CH₃ F 132 3 12 H F133 3 14 CH₃ H

For use in the film-forming composition of the present invention, thefluororesin can be obtained by polymerization of one kind, or two ormore kinds, of the monomer of the general formula (5).

Any monomer other than the monomer of the general formula (5) may beadded to the raw material within the range that does not impair thesolubility of the fluororesin in the fluorine-containing solvent. Theamount of the other monomer added is preferably 10 mass % or less basedon the total mass of the fluororesin.

As such other monomer, there can be used an α-substituted orunsubstituted acrylic ester, α-olefin, fluorine-containing olefin orcarboxylic acid vinyl ester. This other monomer may have at least onehydrogen atom replaced by fluorine. Specific examples of the acrylicester are methyl ester, ethyl ester, propyl ester, isopropyl ester,butyl ester, isobutyl ester, tert-butyl ester, pentyl ester, isopentylester, hexyl ester, cyclohexyl ester, cyclohexyl methyl ester, 2-hydroxyethyl ester, 2-hydroxy propyl ester, 3-hydroxy propyl ester, 4-hydroxycyclohexyl ester, 4-(hydroxymethyl)cyclohexyl methyl ester, bornylester, isobornyl ester, norbornyl ester, methoxymethyl ester,methoxyethyl ester, ethoxyethyl ester, ethoxyethoxyethyl ester andmethoxyethoxyethyl ester of acrylic acid, methacrylic acid,α-fluoroacrylic acid or α-trifluoromethylacrylic acid. Specific examplesof the carboxylic acid vinyl ester are vinyl acetate, vinyl propionate,vinyl butyrate, vinyl caproate, vinyl laurate, vinyl palmitate, vinylstearate, vinyl pivalate, vinyl chloroacetate, vinyl methacrylate andvinyl benzoate.

Preferred examples of the fluororesin used in the film-formingcomposition of the present invention are those having at least one ofthe following repeating units.

[Polymerization Method and Purification Method]

For preparation of the fluororesin, the polymerization of the monomerscan be performed by e.g. a commonly known radical polymerization processand, more specifically, by using a radical initiator such as azocompound, peroxide, persulfuric acid compound or redox compound as aninitiator of the radical reaction.

It is feasible to perform the polymerization by the use of a solvent incombination with the monomers and the polymerization initiator. Variousorganic compounds can be used as the polymerization solvent. Examples ofthe polymerization solvent are: esters such as ethyl acetate, butylacetate and propylene glycol monomethylether acetate; ketones such asacetone, 2-butanone and cyclohexanone; ethers such as diisopropyl ether,dibutyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzeneand toluene; and hydrocarbons such as hexane, heptane and cyclohexane.In each of these solvents, at least one hydrogen atom may be replaced byhalogen. The fluorine-containing solvent usable as the solvent of thefilm-forming composition can also be used as the polymerization solvent.

The concentration of the monomer during the polymerization is preferablyin the range of 1 to 95 mass %, more preferably 10 to 80 mass %, basedon the total mass of the reaction system. When the concentration of themonomer is lower than 1 mass %, the reaction rate of the polymerizationmay be lowered. When the concentration of the monomer exceeds 80 mass %,it may become difficult to prepare the fluororesin due to increase inthe viscosity of the polymerization solution.

It is preferable to reduce remaining unreacted monomer by purificationafter the reaction. The purification can be performed by distillation ofthe remaining monomer under a reduced pressure or under heating,reprecipitation using a poor solvent, liquid-liquid extraction of thepolymerization solution or washing the solid polymerization product bystirring in a solvent. These purification techniques can be used in anycombination thereof.

2. Fluorine-Containing Solvent

In the film-forming composition of the present invention, thefluorine-containing solvent preferably includes a fluorine-containinghydrocarbon or a fluorine-containing ether.

It is preferable that the fluorine-containing solvent includes, as thefluorine-containing hydrocarbon, a C₄-C₈ straight, branched or cyclichydrocarbon in which at least one hydrogen atom is replaced by afluorine atom.

Further, it is preferable that the fluorine-containing solvent includes,as the fluorine-containing ether, a fluorine-containing ether of thegeneral formula (2).R³—O—R⁴  (2)In the general formula (2), R³ and R⁴ each independently represent aC₁-C₁₅ straight, C₃-C₁₅ branched or C₃-C₁₅ cyclic hydrocarbon group; andat least one hydrogen atom of the ether is replaced by a fluorine atom.

The fluorine-containing solvent may preferably further include afluorine-containing alcohol of the general formula (3).R⁵—OH  (3)

In the general formula (3), R⁵ represents a C₁-C₁₅ straight, C₃-C₁₅branched or C₃-C₁₅ cyclic hydrocarbon group in which at least onehydrogen atom is replaced by a fluorine atom.

As the fluorine-containing solvent, there can be used anyfluorine-containing solvent capable of dissolving the fluororesin in thefilm-forming composition of the present invention. There is noparticular limitation on the fluorine content of the fluorine-containingsolvent. In order for the fluorine-containing solvent to quicklydissolve the fluororesin, the fluorine content of thefluorine-containing solvent is generally 50 to 70 mass %, preferably 55to 70 mass %, based on the total mass of the fluorine-containingsolvent. When the fluorine content of the fluorine-containing solventexceeds 70 mass %, the fluororesin may not be sufficiently dissolved inthe fluorine-containing solvent. When the fluorine content of thefluorine-containing solvent is less than 50 mass %, there may occursurface dissolution or swelling of an organic semiconductor film duringthe application or printing of the film-forming composition onto theorganic semiconductor film. The following fluorine-containinghydrocarbon or fluorine-containing ether can suitably be used as thefluorine-containing solvent in the film-forming composition of thepresent invention.

[Fluorine-Containing Hydrocarbon]

The fluorine-containing hydrocarbon is low in ozone depletion potentialand thus is suitably usable as the fluorine-containing solvent in thefilm-forming composition of the present invention. In particular, theC₄-C₈ straight, branched or cyclic hydrocarbon having at least onehydrogen atom replaced by fluorine is preferred for ease of applicationof the film-forming composition.

As such a fluorine-containing hydrocarbon, there can be used anyobtained by replacing at least one hydrogen atom of butane, pentane,hexane, heptane, octane, cyclopentane, cyclohexane etc. by a fluorineatom. Specific examples of the fluorine-containing hydrocarbon solventare CH₃CF₂CH₂CF₃, CF₃CHFCHFCF₂CF₃, CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and afluorine-containing hydrocarbon of the following formula.

The fluorine-containing hydrocarbon needs to have a boiling point higherthan the temperature of a substrate during the application of thefilm-forming composition. The boiling point of the fluorine-containinghydrocarbon is preferably 20° C. or more higher, more preferably 50° C.or more higher, than the application temperature. When the boiling pointof the fluorine-containing hydrocarbon is lower than the substratetemperature during the application of the film-forming composition, itbecomes difficult to form the film with sufficient flatness due to rapidevaporation of the fluorine-containing hydrocarbon during theapplication of the film-forming composition. The boiling point of thefluorine-containing hydrocarbon is preferably 200° C. or lower, morepreferably 180° C. or lower. When the boiling point of thefluorine-containing hydrocarbon is 200° C. or lower, it is easy toevaporate and remove the fluorine-containing hydrocarbon by heating fromthe coating film of the film-forming composition.

The following are examples of the fluorine-containing hydrocarbon havinga preferable boiling point.

CF₃CHFCHFCF₂CF₃ (Vertrel H manufactured by Du Pont-MitsuiFluorochemicals Co., Ltd., boiling point: 55° C.)

Fluorine-containing hydrocarbon of the following formula (Zeorora Hmanufactured by Zeon Corporation, boiling point: 83° C.)

CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ (Asahiklin AC-6000 manufactured by Asahi GlassCo., Ltd., boiling point: 114° C.)Herein, “Vertrel” is a trade name of fluorine-based solvent manufacturedby Du Pont-Mitsui Fluorochemicals Co., Ltd.; “Zeorora” is a trade nameof fluorine-based solvent (HFC) manufactured by Zeon Corporation; and“Asahiklin” is a trade name of fluorine-based solvent manufactured byAsahi Glass Co., Ltd. These trade names are registered as trademarks.

[Fluorine-Containing Ether]

The fluorine-containing ether is low in ozone depletion potential andglobal warming potential and thus is suitably usable as thefluorine-containing solvent. In particular, the fluorine-containingether of the general formula (2) is preferred as the fluorine-containingsolvent.R³—O—R⁴  (2)In the general formula (2), R³ represents a C₁-C₁₅ straight, C₃-C₁₅branched or C₃-C₁₅ cyclic hydrocarbon group in which at least onehydrogen atom may be replaced by a fluorine atom; and R⁴ represents aC₁-C₁₅ straight, C₃-C₁₅ branched or C₃-C₁₅ cyclic hydrocarbon group inwhich at least one hydrogen atom is replaced by a fluorine atom.

For high solubility of the fluororesin, it is preferable that thedivalent groups R³ and R⁴ are not the same as each other in the generalformula (2).

Specific examples of R³ in the general formula (2) are methyl, ethyl,propyl, isopropyl, vinyl, allyl and methyl vinyl. This hydrocarbon groupmay have at least one hydrogen atom replaced by fluorine.

Specific examples of R⁴ in the general formula (2) are those obtained byreplacing at least one hydrogen atom of methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 1-pentyl, 2-pentyl,3-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, 1-heptyl, 2-heptyl, 3-heptyl,1-octyl, 2-octyl, 3-octyl, 1-nonyl, 2-nonyl, 1-decyl, 2-decyl, undecyl,dodecyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclohexylmethyletc. by a fluorine atom. This hydrocarbon group may have an unsaturatedbond.

The fluorine-containing ether needs to have a boiling point higher thanthe temperature of the substrate during the application of thefilm-forming composition. The boiling point of the fluorine-containingether is preferably 20° C. or more higher, more preferably 50° C. ormore higher, than the application temperature. When the boiling point ofthe fluorine-containing ether is lower than the substrate temperatureduring the application of the film-forming composition, it becomesdifficult to form the film with sufficient flatness due to rapidevaporation of the fluorine-containing aliphatic ether during theapplication of the film-forming composition. The boiling point of thefluorine-containing ether is preferably 200° C. or lower, morepreferably 180° C. or lower. When the boiling point of thefluorine-containing ether is 200° C. or lower, it is easy to evaporateand remove the fluorine-containing ether by heating from the coatingfilm of the film-forming composition.

Preferred examples of the fluorine-containing ether are1,1,2,3,3,3-hexafluoro-1-(2,2,2-trifluoroethoxy)propane,1,1,2,3,3,3-hexafluoro-1-(2,2,3,3,3-pentafluoropropoxy)propane,1,1,2,3,3,3-hexafluoro-1-(2,2,3,3-tetrafluoropropoxy)propane and2,2,3,3,3-pentafluoro-1-(1,1,2,2-tetrafluoroethoxy)propane. Thesefluorine-containing ethers can be prepared by a method as disclosed inJapanese Laid-Open Patent Publication No. 2002-201152.

The following are examples of the fluorine-containing ether having apreferable boiling point.C₃F₇OCH₃C₄F₉OCH₃C₄F₉OC₂H₅

These ether compounds are commercially available under the trade namesof Novec 7000, Novec 7100, Novec 7200, Novec 7300, Novec 7500 and Novec7600 from Sumitomo 3M Limited and each can be used for the film-formingcomposition of the present invention. Herein, the trade name “Novec” isregistered as a trademark.

As the fluorine-containing ether having a preferable boiling point,there can also be used those commercially available under the tradenames of “Vertrel Sinera” and “Vertrel Suprion” from Du Pont-MitsuiFluorochemicals Co., Ltd.

[Fluorine-Containing Alcohol]

In the film-forming composition of the present invention, thefluorine-containing solvent may include a fluorine-containing alcohol ofthe general formula (3) in addition to the fluorine-containinghydrocarbon or the fluorine-containing ether so as to further improvethe solubility of the fluororesin in the fluorine-containing solvent.The fluorine-containing alcohol is preferably added in an amount of 45mass % or less, more preferably 30 mass % or less.R⁵—OH  (3)In the general formula (3), R⁴ represents a C₁-C₁₅ straight, C₃-C₁₅branched or C₃-C₁₅ cyclic hydrocarbon group in which at least onehydrogen atom is replaced by a fluorine atom.

It is preferable that, for high chemical stability, a fluorine atom isnot substituted on a carbon atom adjacent to a hydroxyl group in thefluorine-containing alcohol of the general formula (3).

For ease of application of the film-forming composition, R³ ispreferably a C₁-C₈ straight, C₃-C₁₀ branched or C₃-C₁₀ cyclichydrocarbon group having a larger number of fluorine atoms than that ofhydrogen atoms in the fluorine-containing alcohol of the general formula(3).

Specific examples of the hydrocarbon group as R³ are those obtained byreplacing at least one hydrogen atom of methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 1-pentyl, 2-pentyl,3-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, 1-heptyl, 2-heptyl, 3-heptyl,1-octyl, 2-octyl, 3-octyl, cyclopentyl, cyclohexyl, cyclopentylmethyl,cyclohexylmethyl etc. by a fluorine atom.

It is preferable that the fluorine-containing alcohol of the generalformula (3) has a larger number of fluorine atoms than that of hydrogenatoms for high solubility of the fluororesin.

Among the fluorine-containing alcohol of the general formula (3), afluorine-containing alcohol of the general formula (7) or the generalformula (8) is chemically stable and thus is more suitably usable in thefilm-forming composition of the present invention.R⁸—CH₂—OH   (7)In the general formula (7), R⁸ represents a C₁-C₇ straight or C₃-C⁹branched or cyclic fluorine-containing hydrocarbon group.

In the general formula (8), R⁹ and R¹⁰ each independently represents aC₁-C₄ straight, C₃-C₆ branched or C₃-C₆ cyclic hydrocarbon group havinga larger number of fluorine atoms than that of hydrogen atoms.

Specific examples of R⁸ in the general formula (7) are those obtained byreplacing at least one hydrogen atom of methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 1-pentyl, 2-pentyl,3-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, 1-heptyl, 2-heptyl, 3-heptyl,2-octyl, 3-octyl, cyclopentyl, cyclohexyl, cyclopentylmethyl,cyclohexylmethyl etc. by a fluorine atom. Particularly preferred is thehydrocarbon group where the number of fluorine atoms is two or morelarger than that of hydrogen atoms.

In the general formula (8), a C₁-C₃ straight hydrocarbon atom ispreferred as R⁹, R¹⁰ for ease of synthesis. Specific examples of R⁹, R¹⁰are those obtained by replacing at least one hydrogen atom of methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,2-pentyl, 3-pentyl, 2-hexyl, 3-hexyl, cyclopentyl, cyclohexyl,cyclopentylmethyl etc. by a fluorine atom, where the number of fluorineatoms in the hydrocarbon group is larger than that of hydrogen atoms.

The fluorine-containing alcohol needs to have a boiling point higherthan the temperature of the substrate during the application of thefilm-forming composition. The boiling point of the fluorine-containingalcohol is preferably 20° C. or more higher, more preferably 50° C. ormore higher, than the application temperature. When the boiling point ofthe fluorine-containing alcohol is lower than the substrate temperatureduring the application of the film-forming composition, it becomesdifficult to form the film with sufficient flatness due to rapidevaporation of the fluorine-containing aliphatic alcohol during theapplication of the film-forming composition. The boiling point of thefluorine-containing alcohol is preferably 200° C. or lower, morepreferably 180° C. or lower. When the boiling point of thefluorine-containing alcohol is 200° C. or lower, it is easy to evaporateand remove the fluorine-containing alcohol by heating from the coatingfilm of the film-forming composition.

Specific examples of the fluorine-containing alcohol having theabove-ranged boiling point and used in the film-forming composition ofthe present invention are 1,1,1,3,3,3-hexafluoro-2-propanol,2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoropropanol,2,2,3,3,3-pentafluoropropanol, 2,2,3,4,4,4-hexafluorobutanol,2,2,3,3,4,4,4-heptafluorobutanol, 2,2,3,3,4,4,5,5-octafluoropentanol,2,2,3,3,4,4,5,5,5-nonafluoropentanol,3,3,4,4,5,5,6,6,6-notafluorohexanol,2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptanol,2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptanol,3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanol,(1,2,2,3,3,4,4,5-octafluorocyclopentyl)methanol,(1,2,2,3,3,4,4,5-octafluorocyclopentyl)ethanol and2-(1,2,2,3,3,4,4,5-octafluorocyclopentyl)propane-2-ol. These solventsmay be used in the form of a mixture of two or more kinds thereof.

Among the above solvents, 2,2,2-trifluoroethanol,2,2,3,3-tetrafluoropropanol, 2,2,3,4,4,4-hexafluorobutanol and2,2,3,3,4,4,5,5-octafluoropentanol, each of which does not affect theorganic material and sufficiently dissolves the fluororesin in thefilm-forming composition of the present invention, are particularlypreferred as the fluorine-containing alcohol.

[Other Solvent]

For the purpose of viscosity adjustment, boiling point adjustment andadjustment of the solubility of the fluororesin, the solvent may includeany fluorine-free solvent such as alkane, ether, alcohol, ester, ketoneor aromatic hydrocarbon in addition to the fluorine-containinghydrocarbon, the fluorine-containing ether and the fluorine-containingalcohol in the film-forming composition of the present invention. Theamount of the fluorine-free solvent added is preferably 20 mass % orless based on the total mass of the solvent including thefluorine-containing solvent.

For example, there can be used the following solvents having a boilingpoint close to that of the fluorine-containing solvent. The alkane ispreferably a C₅-C₁₂ straight, branched or cyclic alkane. Specificexamples of the alkane are pentane, hexane, heptane, octane, nonane,decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane,methylcyclopentane and methylcyclohexane. The ketone is preferably aC₅-C₁₂ ketone. Specific examples of the ketone are cyclopentanone,cyclohexanone, acetone, 2-butanone, 2-pentanone, 3-pentanone,3-methyl-2-butanone, 2-hexanone, 2-methyl-4-pentanone, 2-heptanone and2-octanone. The ether is preferably a C₄-C₁₆ straight, branched orcyclic ether. Specific examples of the ether are diethyl ether, dipropylether, diisopropyl ether, dibutyl ether, diisobutyl ether, di-tert-butylether, dipentyl ether, diisopentyl ether, dihexyl ether, ethylene glycoldimethyl ether, ethylene glycol diethyl ether, diethylene glycoldimethyl ether, diethylene glycol diethyl ether, triethylene glycoldimethyl ether and triethylene glycol diethyl ether. The alcohol ispreferably is an alcohol obtained by substituting one to three hydroxygroups on a C₁-C₁₀ straight, C₃-C₁₀ branched or C₃-C₁₀ cyclic alkylgroup. Specific examples of the alcohol are methanol, ethanol,1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol,1-pentanol, 2-pentanol, isopentanol, 4-methyl-2-pentanol, 1-hexanol,2-hexanol, ethylene glycol, ethylene glycol monomethyl ether, propyleneglycol, propylene glycol monomethyl ether, propylene glycol monoethylether, diethylene glycol monomethyl ether and diethylene glycolmonoethyl ether. The ester is preferably a C₁-C₁₂ ester. Specificexamples of the ester are methyl acetate, ethyl acetate, propyl acetate,isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate,hexyl acetate, methyl lactate, ethyl lactate, methyl butyrate, ethylbutyrate, propyl butyrate and propylene glycol monomethylether acetate.The aromatic hydrocarbon is preferably a C₆-C₁₂ aromatic hydrocarbon.Specific examples of the aromatic hydrocarbon are benzene, toluene,xylene, ethylbenzene, trimethylbenzene, cumene and diethylbenzene.

[Fluorine-Containing Solvent for Film-Forming Composition]

Preferred examples of the fluorine-containing solvent used in thefilm-forming composition of the present invention are: single solventssuch as C₄F₉OCH₃, C₄F₉OC₂H₅, CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃, Vertrel Suprionand Novec 7300; and mixed solvents such as a mixed solvent of C₄F₉OCH₃and 2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 100:0.01 to70:30, a mixed solvent of C₄F₉OCH₃ and 2,2,2-trifluoroethanol in a massratio of 100:0.01 to 70:30, a mixed solvent of C₄F₉OCH₃ and2,2,3,4,4,4-hexafluorobutanol in a mass ratio of 100:0.01 to 70:30, amixed solvent of C₄F₉OCH₃ and(1,2,2,3,3,4,4,5-octafluorocyclopentyl)ethanol in a mass ratio of100:0.01 to 70:30, a mixed solvent of C₄F₉OCH₂CH₃ and2,2,3,3-tetrafluoropropanol in a mass ratio of 100:0.01 to 70:30, amixed solvent of CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and 2,2,2-trifluoroethanol ina mass ratio of 100:0.01 to 70:30, a mixed solvent ofCF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and 2,2,3,3,4,4,5,5-octafluoropentanol in amass ratio of 100:0.01 to 70:30, a mixed solvent ofCF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and 2,2,3,4,4,4-hexafluorobutanol in a massratio of 100:0.01 to 70:30, a mixed solvent of Vertrel Suprion and2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 100:0.01 to 70:30,a mixed solvent of Novec 7300 and 2,2,3,3-tetrafluoropropanol in a massratio of 100:0.01 to 70:30 and a mixed solvent of Novec 7300 and2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 100:0.01 to 70:30.

3. Film-Forming Composition

[Composition Ratio]

In the film-forming composition of the present invention, the amount ofthe fluororesin used is in the range of 0.1 to 25 parts by mass,preferably 0.5 to 20 parts by mass, per 100 parts by mass of thefluorine-containing solvent. When the amount of the fluororesin used isless than 0.1 parts by mass, the film of the fluororesin may become toosmall to sufficiently cover and protect the organic semiconductorelement. When the amount of the fluororesin used exceeds 25 parts bymass, it may become difficult to form the uniform film of thefluororesin.

It is preferable in the film-forming composition of the presentinvention that: the fluorine content of the fluororesin is in the rangeof 30 to 65 mass %; and the fluorine content of the fluorine-containingsolvent is 50 to 70 mass %. The fluororesin is readily soluble in thefluorine-containing solvent when the fluorine contents are within theabove specific ranges.

The fluorine content of the fluorine-containing solvent is morepreferably in the range of 50 to 70 mass %, still more preferably 55 to70 mass %, in the film-forming composition of the present invention.When the fluorine content of the fluorine-containing solvent exceeds70%, the fluororesin may not be sufficiently dissolved in thefluorine-containing solvent. When the fluorine content of thefluorine-containing solvent is less than 50 mass %, there may occursurface dissolution or swelling of the organic semiconductor film duringthe application or printing of the fluororesin on the organicsemiconductor film.

[Additives]

The film-forming composition of the present invention may include anycomponents, other than the fluororesin and the fluorine-containingsolvent, as additives within the range that does not impair the organicfilm as the application target.

For example, a surfactant or other additive can be added to thefilm-forming composition for the purpose of improving the applicationproperty, leveling property, film-forming property, storage stability,defoaming property etc. of the film-forming composition. Specificexamples of the surfactant are commercially available surfactants suchas those available under the trade name of Megaface F142D, F172, F173,F183 from DIC Corporation, those available under the trade name ofFluorad FC-135, FC-170C, FC-430, FC-431 from Sumitomo 3M Limited, thoseavailable under the trade name of Surflon S-112, S-113, S-131, S-141from AGC Seimi Chemical Co. Ltd., those available under the trade namesof SH-28PA, SH-190, SH-193, SZ-6032 and SF-8428 available from Toray DowCorning Corporation. The amount of the surfactant added is generally 5parts by mass or less per 100 parts by mass of the resin in the resincomposition. Herein, “Megaface” is a trade name of fluorine-basedadditive (surfactant or surface modifier) manufactured by DICCorporation; “Fluorad” is a trade name of fluorosurfactant manufacturedby Sumitomo 3M Limited; and “Surflon” is a trade name offluorosurfactant manufactured by AGC Seimi Chemical Co. Ltd. These tradenames are registered as trademarks.

Further, a curing agent can be added to the film-forming composition.There is no particular limitation on the kind of the curing agent added.There can be used a melamine curing agent, urea curing agent,polybasic-acid curing agent, isocyanate curing agent or epoxy curingagent. Specific examples of the curing agent are: amino compoundsincluding isocyanates such as isophorone diisocyanate, hexamethylenediisocyanate, tolylenediisocyanate and diphenylmethane diisocyanate, andisocyanurates, block isocyanates or buret compounds thereof, melamineresins such as alkylated melamine, methylol melamine and iminomelamine,and urea resins; and epoxy compounds having two or more epoxy groups asobtained by reaction of polyhydric phenol such as bisphenol A withepichlorohydrin. The amount of the curing agent added is generally 35parts by mass or less per 100 parts by mass of the resin in the resincomposition.

4. Organic Semiconductor Film

Next, the organic semiconductor film to be processed using thefilm-forming composition according to the present invention will bedescribed below. The organic semiconductor film can be of any knownorganic semiconductor. Examples of the organic semiconductor are organicsemiconductor materials or organic charge-transfer materials, including:organic low-molecular compounds such as pentacene, anthracene, tetraceneand phthalocyanine; polyacetylene-based conductive polymers;polyphenylene-based conductive polymers such as polyparaphenylene andderivatives thereof, polyphenylene vinylene and derivatives thereof andthe like; heterocyclic conductive polymers such as polypyrrole andderivatives thereof, polythiophene and derivatives thereof, polyfuranand derivatives thereof and the like; and ionic conductive polymers suchas polyaniline and derivatives thereof.

In the manufacturing method of the organic semiconductor elementaccording to the present invention, it is preferable to use any organicsemiconductor material that can be removed by a wet etching processusing a hydrocarbon solvent or aromatic solvent as an etchant. As suchan organic semiconductor material, there can be used: a condensedpolycyclic aromatic hydrocarbon such as anthracene, tetracene orpentacene; organic low-molecular compound such as phthalocyanine;polyacetylene-based conductive polymer; polyphenylene-based conductivepolymer such as polyparaphenylene or derivative thereof, polyphenylenevinylene or derivative thereof or the like; or heterocyclic conductivepolymer such as polypyrrole or derivative thereof, polythiophene orderivative thereof, polyfuran or derivative thereof or the like. Amongothers, the condensed polycyclic aromatic hydrocarbon is particularlypreferably applicable to the manufacturing method of the organicsemiconductor element.

5. Manufacturing Method of Organic Semiconductor Element

In the manufacturing method of the organic semiconductor element, thefluororesin film is formed on the organic semiconductor film in order toprotect the organic semiconductor film during the fine processing of theorganic semiconductor film into a desired semiconductor circuit.

For manufacturing of the organic semiconductor element, the organicsemiconductor circuit is formed by transferring a predetermined patternto the fluororesin film by photolithography, printing process such asrelief printing, intaglio printing, planographic printing, screenprinting or imprint process, and then, etching the organic semiconductorfilm through the pattern of the fluororesin film.

First, an explanation will be given of the patterning of the fluororesinfilm formed from the film-forming composition of the present invention.

In the present invention, the fluororesin film is applied by wet coatingof the film-forming composition to the organic semiconductor film on thesubstrate. The fluororesin film can be patterned by a photolithographyprocess, print process or imprint process. By wet-etching the organicsemiconductor film with the hydrocarbon solvent or aromatic solventafter the patterning of the fluororesin film on the organicsemiconductor film, the pattern of the fluororesin film is transferredto the organic semiconductor film. It is thus possible in the presentinvention to achieve fine processing of the organic semiconductor film.

It is feasible in the present invention to directly form a pattern ofprotection film from the film-forming composition on the organicmaterial by a print process or ink-jet process and then transfer thepattern of the protection film to the organic material by a wet etchingprocess using a hydrocarbon solvent or aromatic solvent. In the case ofdirectly forming the pattern of the protection film by the print processor ink-jet process, the film-forming composition is used as an ink. Asthe printing process, there can be used relief printing, intaglioprinting, gravure printing, planographic printing, screen printing, heattransfer printing or reverse offset printing.

When the aromatic solvent is used as the etchant, the fluororesin filmneeds to be insoluble or difficult to dissolve in the etchant during theetching. After the etching, the fluororesin film is removed from or lefton the resulting organic semiconductor circuit. It is desired that, whenthe fluororesin film is removed from the organic semiconductor circuit,the fluororesin film does not cause a deterioration of the organicsemiconductor circuit. It is desired that, when the fluororesin film isleft on the organic semiconductor circuit, the fluororesin film servesas an insulating film so as not to cause a short circuit of the organicsemiconductor circuit.

In the case of processing an organic semiconductor film into a circuitpattern, a film-forming composition and a film formed therefrom forprotection of the organic semiconductor circuit are required to satisfythe following conditions: (1) the film can be easily formed on theorganic semiconductor film; (2) the film can be removed from the organicsemiconductor pattern without causing a deterioration or short circuitof the organic semiconductor circuit; (3) the film has an insulatingproperty so as not to impair the electrical characteristics of theorganic semiconductor circuit; and (4) the film does not readily becomeaffected by an aromatic solvent as an etchant.

The fluororesin film formed from the film-forming composition of thepresent invention can be removed as required by dissolution in aspecific fluorine-containing solvent. For dissolution and removal of thefluororesin film, it is feasible to use the same fluorine-containingsolvent as that of the film-forming composition as long as the influenceof the solvent on the organic semiconductor is small. Alternatively, adifferent fluorine-containing solvent may be used to e.g. secure highersolubility of the fluororesin film.

There are some methods for dissolution and removal of the fluororesinfilm formed from the film-forming composition on the substrate,including immersion of the substrate in the fluorine-containing solvent,washing of the substrate by pouring the fluorine-containing solventwhile holding the substrate in a vertical or inclined manner or rotatingthe substrate by a spin coater, or placement of the substrate undersaturated vapor of the fluorine-containing solvent in a chamber. Theamount of the fluorine-containing solvent used for dissolution andremoval of the fluororesin film is preferably 5 times or more larger,more preferably 10 times or more larger, than the total mass of thefluororesin film. When the amount of the fluorine-containing solventused is small, the fluororesin film cannot be removed sufficiently. Thefluororesin film formed from the film-forming composition of the presentinvention has an insulating property and, even when remains in theorganic semiconductor element without dissolution and removal, does notimpair the electrical characteristics of the semiconductor circuit.

[Example of Manufacturing of Organic Semiconductor Element]

One example of the manufacturing method of the organic semiconductorelement using the film-forming composition according to the presentinvention will be described in detail below with reference to FIG. 1. Itshould be however noted that the manufacturing method of the organicsemiconductor element using the film-forming composition is not limitedto this example.

First, an organic semiconductor film 2 is formed on a substrate 1 asshown in FIG. 1(A) by application or vapor deposition of an organicsemiconductor solution.

Next, a fluororesin film 3 is formed on the organic semiconductor film 2as shown in FIG. 1(B) by application of the film-forming composition ofthe present invention.

The film-forming composition can be applied by e.g. dip coating, spraycoating, spin coating, bar coating, applicator or roll coater. Thecoating film of the film-forming composition as applied to the organicsemiconductor film 2 contains the solvent. The fluororesin film 3 isthus obtained by subjecting the coating film to air drying.

The substrate 1 is then heated for baking of the fluororesin film 3.During the baking, the heating temperature is 250° C. or lower. There isno need to heat the fluororesin film at a temperature higher than 250°C. The heating temperature is varied depending on the boiling point ofthe solvent and is preferably in the range of 10 to 150° C. When theheating temperature is lower than 10° C., it takes long time to dry thefluororesin film. When the heating temperature is higher than 150° C.,the surface flatness of the fluororesin film 3 may be impaired. Further,the heating time is in the range of 30 seconds to 15 minutes. When theheating time is shorter than 30 seconds, the solvent may remain in thefluororesin film. There is no need to heat the fluororesin film forlonger than 15 minutes.

The fluororesin film 3 is subsequently patterned, as shown in FIG. 1(C),by a lithography process, imprint process, print process such as reliefprinting, intaglio printing, gravure printing, planographic printing,screen printing, heat transfer printing or reverse offset printing, orink-jet process.

In the case of patterning the fluororesin film 3 by the lithographyprocess, a photoresist film is first formed on the fluororesin filmalthough not shown in the drawing. The photoresist film can be formed byapplying a photoresist with a solvent that does not affect thefluororesin film 3 or by adhering a dry film resist. When thephotoresist film is formed by application of the photoresist, it ispreferable to use a hydrocarbon solvent or aromatic solvent that doesnot affect the fluororesin film 3. The photoresist film is exposedthrough a photo mask and thereby processed into a photoresist pattern.Then, the fluororesin film 3 is patterned by wet etching with an etchantsolvent, reactive ion etching or gas etching.

In the case of patterning the fluororesin film 3 by the print process, apattern is transferred from a printing original plate to the fluororesinfilm 3. The pattern can be transferred by pressing projections anddepressions of the printing original plate against the fluororesin film3 or by pressing only projections of the printing original plate againstthe fluororesin film 3 and thereby removing the corresponding regions ofthe fluororesin film 3. When the pattern of the printing original plateis transferred to the fluororesin film 3, it is preferable to soften thefluororesin film 3 by heating or solvent swelling and thereby easilychange the shape of the fluororesin film 3.

In the case of patterning the fluororesin film 3 by the ink-jet process,an etching resistant material is ink-jetted onto regions of thefluororesin film 3 to be left. Then, the fluororesin film 3 is patternedby etching uncoated regions of the fluororesin film 3. For suchpatterning, there can be used wet etching using a solvent, reactive ionetching or gas etching.

At this time, the substrate 1 may be heated for baking of the patternedfluororesin film 3. During the baking, the heating temperature is 250°C. or lower. There is no need to heat the fluororesin film at atemperature higher than 250° C. The heating temperature is varieddepending on the boiling point of the solvent and is preferably in therange of 10 to 150° C. When the heating temperature is lower than 10°C., it takes long time to dry the fluororesin film. When the heatingtemperature is higher than 150° C., the surface flatness of thefluororesin film 3 may be impaired. The heating time is in the range of30 seconds to 15 minutes. When the heating time is shorter than 30seconds, the solvent may remain in the fluororesin film. There is noneed to heat the fluororesin film for longer than 15 minutes. Thepatterned fluororesin film 3 serves as a protection on regions of theorganic resin film 2 to be patterned during the subsequent wet etchingstep.

After that, the organic semiconductor film 2 is wet-etched into apattern 2 b as shown in FIG. 1(D). More specifically, any regions of theorganic semiconductor film 2 which are not covered by the patternedfluororesin film 3 are dissolved and removed by immersing the laminateof the substrate 1, the organic semiconductor film 2 and the patternedfluororesin film 3 in the hydrocarbon solvent or aromatic solvent or bypouring the hydrocarbon solvent or aromatic solvent over the laminate ofthe substrate 1, the organic semiconductor film 2 and the patternedfluororesin film 3. By this, the pattern of the fluororesin film 3 istransferred to the organic semiconductor film 2 and obtained as thepattern 2 b.

As shown in FIG. 1(E), it is feasible to remove the fluororesin film 3by dissolution in a fluorine-containing solvent. There can be used thesame fluorine-containing solvent as that of the film-formingcomposition. The fluororesin film can be dissolved and removed byimmersing the substrate 1 in the fluorine-containing solvent, by pouringthe fluorine-containing solvent film over the substrate 1 while holdingthe substrate 1 in a vertical or inclined manner or rotating thesubstrate 1 by a spin coater, or by placing the substrate 1 undersaturated vapor of the fluorine-containing solvent in a chamber. Thefluororesin film 3 may alternatively remain as an interlayer insulatingfilm.

6. Device Cleaning Method

The fluororesin contained in the film-forming composition for formationof the fluororesin film is soluble in a ketone, ether or carboxylic acidester. The application equipment used for formation of the fluororesinfilm 3 can be thus cleaned by such an organic solvent. The cleaningmethod is determined depending on the shape and environment of theequipment. It is feasible to clean the equipment by immersing theequipment in the organic solvent, by spraying the organic solvent ontothe equipment and then flowing the organic solvent away from theequipment, or by spraying the organic solvent onto the equipment andthen wiping the organic solvent off the equipment.

7. Effects of the Invention

As mentioned above, the film-forming composition of the presentinvention is characterized by containing: the specificfluorine-containing solvent that does not cause dissolution or swellingof the organic material: and the specific fluororesin soluble in thefluorine-containing solvent.

The film-forming composition of the present invention, when applied tothe organic semiconductor film, does not affect the organicsemiconductor film by dissolution or swelling. The fluororesin film canbe thus formed from the film-forming composition on the organicsemiconductor film by a wet process. Further, the fluororesin film canbe patterned by a photolithography process, print process or imprintprocess and remain unaffected by the etchant such as hydrocarbon solventor aromatic solvent during the wet etching of the organic semiconductorfilm. When the film-forming composition of the present invention isapplied to the organic semiconductor film, the fluorine-containingsolvent of the film-forming composition does not cause dissolution orswelling of the organic semiconductor film. The fluororesin film can bethus formed from the film-forming composition on the organic material bya wet process. Further, the fluororesin film can be patterned by aphotolithography process, print process or imprint process and does notbecome affected by the etchant such as hydrocarbon solvent or aromaticsolvent during the wet etching of the organic semiconductor film. Inthis way, it is possible by using the film-forming composition of thepresent invention to form a semiconductor circuit pattern by fineprocessing of the organic semiconductor film on the substrate. Thefilm-forming composition of the present invention is therefore suitablyusable for the manufacturing of the organic semiconductor element.

Moreover, the fluororesin film is suitably applicable as an interlayerinsulating film in the organic semiconductor element as the fluororesinof the film-forming composition has an adequate glass transitiontemperature, easy processability, easy film-forming property and highheat resistance.

EXAMPLES

The present invention will be described in more detail below by way ofthe following examples. It should be however noted that the followingexamples are not intended to limit the present invention thereto.

Synthesis of Fluororesins

Unless otherwise mentioned, fluororesins for film-forming compositionswere prepared by the following method.

A 50-mL egg-shaped flask of glass was used as a reaction vessel. Anacrylic acid ester derivative, 2-butanone as a polymerization solventand dimethyl-2,2-azobis(2-methylpropionate) (available under the tradename of “V-601” from Wako Pure Chemical Industries, Ltd.) as aninitiator were weighed in predetermined amounts and put into thereaction vessel. A cooling pipe was attached to the reaction vessel. Theinside of the reaction vessel was replaced with nitrogen through thecooling pipe while stirring the content of the reaction vessel. Then,the reaction vessel was heated in an oil bath of 80° C. for 6 hours.After the heating, the resulting reaction solution was concentrated by arotary evaporator to 1.5 times the total mass of the monomer used. Theconcentrated solution was mixed with as much heptane as 15 times thetotal mass of the monomer used, thereby forming a precipitate. Theprecipitate was filtered out and dried by heating at 65° C. in a dryingmachine as vacuumed by an oil pump. By this, the target fluororesin wasobtained.

The weight-average molecular weight Mw and molecular weight distribution(Mw/Mn; division of the molecular-average molecular weight by thenumber-average molecular weight) of the fluororesin was measured by gelpermeation chromatography (GPC). The GPC was herein performed using aGPC analyzer: model “HLC-8320” manufactured by Tosoh Corporation with aseries connection of three columns (trade name “TSKgel GMH_(XL)”manufactured by Tosoh Corporation), tetrahydrofuran as a developingsolvent and a refractive index detector as a detector. The fluorinecontent of the fluororesin were determined based on a F¹⁹-NMR spectrumas measured by a nuclear magnetic resonance spectrometer (model “JNM-ECA400” manufactured by JEOL Ltd.). More specifically, 25 to 35 mg of thefluororesin and 5 to 10 mg of 1,4-bis(trifluoromethyl)benzene asinternal reference substance were weighed and dissolved in 0.9 g ofdeuterated chloroform. The F¹⁹-NMR spectrum of the resulting solutionwas measured. Further, the amount of the acrylic acid esterderivative-derived repeating unit in the fluororesin was determined byconversion of the ratio between the peak intensity of the acrylic acidester derivative and the peak intensity of the internal referencesubstance in the F¹⁹-NMR spectrum.

Fluororesin Synthesis Example 1

In a reaction vessel, 5.00 g (25.0 mmol) of 2,2,3,3-tetrafluoropropylmethacrylate, 10.0 g of butanone and 0.575 g (2.50 mmol) of initiatorwere placed. The resulting solution was subjected to radicalpolymerization by the method described in the above section “Synthesisof Fluororesins”. As a result, there was obtained 4.90 g of fluororesin1 having a repeating unit of the following formula (9). The yield of thefluororesin 1 relative to the total mass of the monomer used was 98 mass%. The weight-average molecular weight Mw of the fluororesin 1 was11,000. The molecular weight distribution Mw/Mn of the fluororesin 1 was1.34. The fluorine content of the fluororesin 1 was 38 mass %.

Fluororesin Synthesis Example 2

In a reaction vessel, 5.00 g (16.7 mmol) of2,2,3,3,4,4,5,5-octafluoropentyl methacrylate, 10.0 g of butanone and0.384 g (1.67 mmol) of initiator were placed. The resulting solution wassubjected to radical polymerization by the method described in the abovesection “Synthesis of Fluororesins”. As a result, there was obtained4.90 g of fluororesin 2 having a repeating unit of the following formula(10). The yield of the fluororesin 2 relative to the total mass of themonomer used was 80 mass %. The weight-average molecular weight Mw ofthe fluororesin 2 was 5,000. The molecular weight distribution Mw/Mn ofthe fluororesin 2 was 1.67. The fluorine content of the fluororesin 2was 51 mass %.

Fluororesin Synthesis Example 3

In a reaction vessel, 5.00 g (12.5 mmol) of2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl methacrylate, 10.0 g ofbutanone and 0.288 g (1.25 mmol) of initiator were placed. The resultingsolution was subjected to radical polymerization by the method describedin the above section “Synthesis of Fluororesins”. As a result, there wasobtained 3.65 g of fluororesin 3 having a repeating unit of thefollowing formula (11). The yield of the fluororesin 3 relative to thetotal mass of the monomer used was 73 mass %. The weight-averagemolecular weight Mw of the fluororesin 3 was 13,000. The molecularweight distribution Mw/Mn of the fluororesin 3 was 1.49. The fluorinecontent of the fluororesin 3 was 57 mass %.

Fluororesin Synthesis Example 4

In a reaction vessel, 5.00 g (22.9 mmol) of 2,2,3,3,3-pentafluoropropylmethacrylate, 10.0 g of butanone and 0.528 g (2.29 mmol) of initiatorwere placed. The resulting solution was subjected to radicalpolymerization by the method described in the above section “Synthesisof Fluororesins”. As a result, there was obtained 2.70 g of fluororesin4 having a repeating unit of the following formula (12). The yield ofthe fluororesin 4 relative to the total mass of the monomer used was 54mass %. The weight-average molecular weight Mw of the fluororesin 4 was9,500. The molecular weight distribution Mw/Mn of the fluororesin 4 was1.48. The fluorine content of the fluororesin 4 was 44 mass %.

Fluororesin Synthesis Example 5

In a reaction vessel, 5.00 g (18.6 mmol) of2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 10.0 g of butanone and0.429 g (1.86 mmol) of initiator were placed. The resulting solution wassubjected to radical polymerization by the method described in the abovesection “Synthesis of Fluororesins”. As a result, there was obtained3.40 g of fluororesin 5 having a repeating unit of the following formula(13). The yield of the fluororesin 5 relative to the total mass of themonomer used was 68 mass %. The weight-average molecular weight Mw ofthe fluororesin 5 was 11,000. The molecular weight distribution Mw/Mn ofthe fluororesin 5 was 1.35. The fluorine content of the fluororesin 5was 50 mass %.

Fluororesin Synthesis Example 6

In a reaction vessel, 5.00 g (15.7 mmol) of2,2,3,3,4,4,5,5,5-nonafluoropentyl methacrylate, 10.0 g of butanone and0.362 g (1.57 mmol) of initiator were placed. The resulting solution wassubjected to radical polymerization by the method described in the abovesection “Synthesis of Fluororesins”. As a result, there was obtained3.20 g of fluororesin 6 having a repeating unit of the following formula(14). The yield of the fluororesin 6 relative to the total mass of themonomer used was 64 mass %. The weight-average molecular weight Mw ofthe fluororesin 6 was 6,400. The molecular weight distribution Mw/Mn ofthe fluororesin 6 was 1.32. The fluorine content of the fluororesin 6was 54 mass %.

Fluororesin Synthesis Example 7

In a reaction vessel, 5.00 g (15.1 mmol) of3,3,4,4,5,5,6,6,6-nonafluorohexyl methacrylate, 10.0 g of butanone and0.347 g (1.51 mmol) of initiator were placed. The resulting solution wassubjected to radical polymerization by the method described in the abovesection “Synthesis of Fluororesins”. As a result, there was obtained3.25 g of fluororesin 7 having a repeating unit of the following formula(15). The yield of the fluororesin 7 relative to the total mass of themonomer used was 65 mass %. The weight-average molecular weight Mw ofthe fluororesin 7 was 13,000. The molecular weight distribution Mw/Mn ofthe fluororesin 7 was 1.49. The fluorine content of the fluororesin 7was 52 mass %.

Fluororesin Synthesis Example 8

In a reaction vessel, 5.00 g (11.7 mmol) of3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate, 10.0 g ofbutanone and 0.266 g (1.17 mmol) of initiator were placed. The resultingsolution was subjected to radical polymerization by the method describedin the above section “Synthesis of Fluororesins”. As a result, there wasobtained 3.30 g of fluororesin 8 having a repeating unit of thefollowing formula (16). The yield of the fluororesin 8 relative to thetotal mass of the monomer used was 66 mass %. The weight-averagemolecular weight Mw of the fluororesin 8 was 4,900. The molecular weightdistribution Mw/Mn of the fluororesin 8 was 1.13. The fluorine contentof the fluororesin 8 was 57 mass %.

Fluororesin Synthesis Example 9

In a reaction vessel, 5.00 g (21.2 mmol) of1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 10.0 g of butanone and0.488 g (2.12 mmol) of initiator were placed. The resulting solution wassubjected to radical polymerization by the method described in the abovesection “Synthesis of Fluororesins”. As a result, there was obtained1.70 g of fluororesin 9 having a repeating unit of the following formula(17). The yield of the fluororesin 9 relative to the total mass of themonomer used was 34 mass %. The weight-average molecular weight Mw ofthe fluororesin 9 was 5,000. The molecular weight distribution Mw/Mn ofthe fluororesin 9 was 1.64. The fluorine content of the fluororesin 9was 48 mass %.

Fluororesin Synthesis Example 10

In a reaction vessel, 10.00 g (45.0 mmol) of1,1,1,3,3,3-hexafluoroisopropyl acrylate, 10.0 g of butanone and 1.037 g(4.50 mmol) of initiator were placed. The resulting solution wassubjected to radical polymerization by the method described in the abovesection “Synthesis of Fluororesins”. As a result, there was obtained9.00 g of fluororesin 10 having a repeating unit of the followingformula (18). The yield of the fluororesin 10 relative to the total massof the monomer used was 90 mass %. The weight-average molecular weightMw of the fluororesin 10 was 29,000. The molecular weight distributionMw/Mn of the fluororesin 10 was 3.00. The fluorine content of thefluororesin 10 was 51 mass %.

Fluororesin Synthesis Example 11

In a reaction vessel, 5.15 g (21.8 mmol) of1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 4.85 g (21.8 mmol) of1,1,1,3,3,3-hexafluoroisopropyl acrylate, 10.0 g of butanone and 0.804 g(3.49 mmol) of initiator were placed. The resulting solution wassubjected to radical polymerization by the method described in the abovesection “Synthesis of Fluororesins”. As a result, there was obtained9.30 g of fluororesin 11 having repeating units of the following formula(19). The yield of the fluororesin 11 relative to the total mass of themonomers used was 93 mass %. The weight-average molecular weight Mw ofthe fluororesin 11 was 5,400. The molecular weight distribution Mw/Mn ofthe fluororesin 11 was 1.86. The fluorine content of the fluororesin 11was 50 mass %.

Fluororesin Synthesis Example 12

In a reaction vessel, 3.97 g (16.8 mmol) of1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 1.03 g (7.24 mmol) ofbutyl methacrylate, 10.0 g of butanone and 0.111 g (0.482 mmol) ofinitiator were placed. The resulting solution was subjected to radicalpolymerization by the method described in the above section “Synthesisof Fluororesins”. As a result, there was obtained 3.47 g of fluororesin12 having repeating units of the following formula (20). The yield ofthe fluororesin 12 relative to the total mass of the monomers used was69 mass %. The weight-average molecular weight Mw of the fluororesin 12was 6,600. The molecular weight distribution Mw/Mn of the fluororesin 12was 1.47. The fluorine content of the fluororesin 12 was 38 mass %.

Fluororesin Synthesis Example 13

In a reaction vessel, 3.88 g (16.4 mmol) of1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 1.12 g (7.08 mmol) of2-ethoxyethyl methacrylate, 10.0 g of butanone and 0.115 g (0.499 mmol)of initiator were placed. The resulting solution was subjected toradical polymerization by the method described in the above section“Synthesis of Fluororesins”. As a result, there was obtained 3.91 g offluororesin 13 having a repeating unit of the following formula (21).The yield of the fluororesin 13 relative to the total mass of themonomers used was 78 mass %. The weight-average molecular weight Mw ofthe fluororesin 13 was 16,000. The molecular weight distribution Mw/Mnof the fluororesin 12 was 1.65. The fluorine content of the fluororesin12 was 38 mass %.

Comparative Resin Synthesis Example 1

In a reaction vessel, 5.00 g (35.2 mmol) of n-butyl methacrylate, 10.0 gof butanone and 0.162 g (0.704 mmol) of initiator were placed. Theresulting solution was subjected to radical polymerization by the methoddescribed in the above section “Synthesis of Fluororesins”. As a result,there was obtained 0.88 g of fluororesin 14 having a repeating unit ofthe following formula (22). The weight-average molecular weight Mw ofthe fluororesin 14 was 16,000. The molecular weight distribution Mw/Mnof the fluororesin 14 was 1.48. The yield of the fluororesin 14 relativeto the total mass of the monomer used was 18 mass %.

Comparative Resin Synthesis Example 2

In a reaction vessel, 10.00 g (63.2 mmol) of 2-ethoxyethyl methacrylate,10.0 g of butanone and 0.225 g (0.977 mmol) of initiator were placed.The resulting solution was subjected to radical polymerization by themethod described in the above section “Synthesis of Fluororesins”. As aresult, there was obtained 6.21 g of fluororesin 15 having a repeatingunit of the following formula (23). The weight-average molecular weightMw of the fluororesin 15 was 8,000. The molecular weight distributionMw/Mn of the fluororesin 15 was 1.45. The yield of the fluororesin 15relative to the total mass of the monomer used was 62 mass %.

[Evaluation Test on Solubility of Fluororesins in Fluorine-ContainingSolvents]

The fluororesins 1 to 13, the comparative fluorine-free resins 14 and 15and polymethyl methacrylate (hereinafter sometimes referred to as“PMMA”; polystyrene-conversion weight-average molecular weight: 15,000)available from Sigma-Aldrich Co. LLC were tested for the solubility invarious fluorine-containing solvents.

<Evaluation Method>

The solubility of the fluororesin was evaluated by mixing 10 mass % ofthe fluororesin as a solute in each solvent at room temperature andvisually checking whether the solute was dissolved in the solventwithout solid deposition or suspension or there was seen an insolublematter by solid deposition or suspension.

<Evaluation Results>

The evaluation results are shown in TABLES 4 to 19. TABLES 4 to 16 showthe evaluation results on the solubility of the fluororesins 1 to 13according to the present invention in the various fluorine-containingsolvents; TABLE 17 shows the evaluation results on the solubility of thecomparative fluorine-free resin 14 (Comparative Examples 1 to 4); TABLE18 shows the evaluation results on the solubility of the comparativefluorine-free resin 15 (Examples 5 to 8); and TABLE 19 shows theevaluation results on the solubility of the PMMA (Comparative Examples 9to 11).

The fluororesins 1 to 13 were soluble in the fluorine-containingsolvents as shown in TABLES 4 to 16. On the other hand, the comparativefluorine-free resins 14 and 15 were insoluble in fluorine-containingsolvents as shown in TABLES 17 and 18. The PMMA was also insoluble influorine-containing solvents as shown in TABLE 19. In each table,“Novec” is a trade name of hydrofluoroether (HFE) manufactured bySumitomo 3M Limited; and “Vertrel Suprion” is a trade name offluorine-based solvent manufactured by Du Pont-Mitsui FluorochemicalsCo., Ltd. These trade names are registered as trademarks.

TABLE 4 Evaluation results on Solubility of Fluororesin 1 SolventEvaluation Example 1 A mixed solvent of C₄H₉OCH₃ and Soluble2,2,2-trifluoroethanol in a mass ratio of 7:3

TABLE 5 Evaluation results on Solubility of Fluororesin 2 SolventEvaluation Example 2 CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ Soluble

TABLE 6 Evaluation results on Solubility of Fluororesin 3 SolventEvaluation Example 3 CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ Soluble Example 4 A mixedsolvent of CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and 2,2,2-trifluoroethanol in a massratio of 7:3 Example 5 Vertrel Suprion Example 6 A mixed solvent ofC₄H₉OCH₃ and 2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 7:3

TABLE 7 Evaluation results on Solubility of Fluororesin 4 SolventEvaluation Example 7 CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ Soluble Example 8 A mixedsolvent of CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 7:3 Example 9C₄H₉OCH₃ Example 10 Vertrel Suprion Example 11 A mixed solvent of Novec7300 and 2,2,3,3-tetrafluoropropanol in a mass ratio of 7:3

TABLE 8 Evaluation results on Solubility of Fluororesin 5 SolventEvaluation Example 12 CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ Soluble Example 13 Amixed solvent of CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and 2,2,2-trifluoroethanol ina mass ratio of 7:3 Example 14 Novec 7300 Example 15 C₄F₉OC₂H₅ Example16 Vertrel Suprion Example 17 A mixed solvent of Vertrel Suprion and2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 7:3

TABLE 9 Evaluation results on Solubility of Fluororesin 6 SolventEvaluation Example 18 CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ Soluble Example 19 Amixed solvent of CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 7:3 Example 20Novec 7300 Example 21 A mixed solvent of C₄H₉OCH₃ and2,2,3,4,4,4-hexafluorobutanol in a mass ratio of 7:3

TABLE 10 Evaluation results on Solubility of Fluororesin 7 SolventEvaluation Example 22 A mixed solvent of SolubleCF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and 2,2,3,3,4,4,5,5-octafluoropentanol in amass ratio of 7:3 Example 23 C₄F₉OCH₂CH₃ Example 24 Vertrel SuprionExample 25 A mixed solvent of C₄H₉OCH₃ and2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 7:3

TABLE 11 Evaluation results on Solubility of Fluororesin 8 SolventEvaluation Example 26 CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ Soluble Example 27 Amixed solvent of CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and2,2,3,4,4,4-hexafluorobutanol in a mass ratio of 7:3 Example 28 Novec7300 Example 29 Vertrel Suprion Example 30 A mixed solvent of C₄F₉OCH₃and (1,2,2,3,3,4,4,5- octafluorocyclopentyl)ethanol in a mass ratio of7:3

TABLE 12 Evaluation results on Solubility of Fluororesin 9 SolventEvaluation Example 31 A mixed solvent of SolubleCF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and 2,2,3,3,4,4,5,5-octafluoropentanol in amass ratio of 7:3 Example 32 C₄F₉OCH₂CH₃ Example 33 Novec 7300 Example34 Vertrel Suprion Example 35 A mixed solvent of C₄F₉OCH₃ and2,2,2-trifluoroethanol in a mass ratio of 7:3 Example 36 A mixed solventof C₄F₉OCH₂CH₃ and 2,2,3,3-tetrafluoropropanol in a mass ratio of 7:3Example 37 A mixed solvent of Novec 7300 and2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 7:3

TABLE 13 Evaluation results on Solubility of Fluororesin 10 SolventEvaluation Example 38 CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ Soluble Example 39 Amixed solvent of CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and 2,2,2-trifluoroethanol ina mass ratio of 7:3 Example 40 C₄F₉OCH₂CH₃ Example 41 Vertrel SuprionExample 42 A mixed solvent of C₄F₉OCH₂CH₃ and2,2,3,3-tetrafluoropropanol in a mass ratio of 7:3 Example 43 A mixedsolvent of Vertrel Suprion and 2,2,3,3,4,4,5,5-octafluoropentanol in amass ratio of 7:3

TABLE 14 Evaluation results on Solubility of Fluororesin 11 SolventEvaluation Example 44 CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ Soluble Example 45 Amixed solvent of CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and 2,2,2-trifluoroethanol ina mass ratio of 7:3 Example 46 C₄F₉OCH₂CH₃ Example 47 Vertrel SuprionExample 48 A mixed solvent of C₄F₉OCH₂CH₃ and2,2,3,3-tetrafluoropropanol in a mass ratio of 7:3 Example 49 A mixedsolvent of Vertrel Suprion and 2,2,3,3,4,4,5,5-octafluoropentanol in amass ratio of 7:3

TABLE 15 Evaluation results on Solubility of Fluororesin 12 SolventEvaluation Example 50 A mixed solvent of SolubleCF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and 2,2,2-trifluoroethanol in a mass ratio of7:3 Example 51 C₄F₉OCH₂CH₃ Example 52 Vertrel Suprion Example 53 A mixedsolvent of C₄F₉OCH₂CH₃ and 2,2,3,3-tetrafluoropropanol in a mass ratioof 7:3 Example 54 A mixed solvent of Vertrel Suprion and2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 7:3

TABLE 16 Evaluation results on Solubility of Fluororesin 13 SolventEvaluation Example 55 A mixed solvent of SolubleCF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and 2,2,2-trifluoroethanol in a mass ratio of7:3 Example 56 C₄F₉OCH₂CH₃ Example 57 Vertrel Suprion Example 58 A mixedsolvent of C₄F₉OCH₂CH₃ and 2,2,3,3-tetrafluoropropanol in a mass ratioof 7:3 Example 59 A mixed solvent of Vertrel Suprion and2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 7:3

TABLE 17 Evaluation results on Solubility of Comparative Resin 14Solvent Evaluation Comparative CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ Solid Example 1Deposition Comparative A mixed solvent of Solid Example 2CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and Deposition2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 7:3 ComparativeNovec 7300 Solid Example 3 Deposition Comparative A mixed solvent ofNovec 7300 and Suspension Example 4 2,2,3,3,4,4,5,5-octafluoropentanolin a mass ratio of 7:3

TABLE 18 Evaluation results on Solubility of Comparative Resin 15Solvent Evaluation Comparative CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ Solid Example 5Deposition Comparative A mixed solvent of Solid Example 6CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ and Deposition2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 7:3 ComparativeVertrel Suprion Suspension Example 7 Comparative A mixed solvent ofVertrel Suprion and Suspension Example 82,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 7:3

TABLE 19 Evaluation results on Solubility of PMMA Solvent EvaluationComparative CF₃CF₂CF₂CF₂CF₂CH₂CH₂CH₃ Solid Deposition Example 9Comparative C₄F₉OCH₂CH₃ Solid Deposition Example 10 Comparative A mixedsolvent of C₄F₉OCH₂CH_(3 and) Solid Deposition Example 112,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 7:3

[Evaluation Test on Cleanability of Film-Forming Compositions]

<Evaluation Method>

Fluororesin films containing the fluororesins 1 to 13 obtained inSynthesis Examples 1 to 13 were tested for the cleanability in threekinds of fluorine-free solvents: 2-butanone, propylene glycol monomethylether acetate and ethyl acetate (Examples 60 to 72). Herein, thefluororesin films were formed from film-forming compositions each usinga mixed solvent of Novec 7300, Vertrel Suprion and2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 3:3:4. The resinconcentrations of the respective film-forming compositions were set to10 mass %.

More specifically, each of the film-forming compositions containing thefluororesins 1 to 13 was applied to a silicon substrate. The thus-coatedsubstrate was immersed in the cleaning solvent. After a lapse of 30seconds, the substrate was taken out of the cleaning solvent and died byair blowing. Then, the substrate was analyzed by an optical interferencefilm thickness meter (model “FTP 300” manufactured by SentechInstruments, Germany) to check whether there was a residue of the filmon the substrate. The film-forming composition was evaluated as“cleanable” when there was seen no film residue.

<Evaluation Results>

The evaluation results are shown in TABLE 20. As shown in TABLE 20, allof the fluororesins 1 to 13 were cleanable by the three kinds offluorine-free cleaning solvents with no film residue.

TABLE 20 Kind of Resin 2-Butanone PGMEA Ethyl Acetate Example 60Fluororesin 1 No film No film No film Example 61 Fluororesin 2 residueresidue residue Example 62 Fluororesin 3 Example 63 Fluororesin 4Example 64 Fluororesin 5 Example 65 Fluororesin 6 Example 66 Fluororesin7 Example 67 Fluororesin 8 Example 68 Fluororesin 9 Example 69Fluororesin 10 Example 70 Fluororesin 11 Example 71 Fluororesin 12Example 72 Fluororesin 13 PGMA: propylene glycol monomethyl etheracetate

[Evaluation Test on Resistance of Fluororesins to Wet-Etching Solvents]

<Evaluation Method>

Fluororesin films containing the fluororesins 1 to 3, films containingthe comparative fluorine-free resins 14 and 15 and film containing PMMAwere tested for the resistance to wet-etching solvents. Morespecifically, the fluororesin films were formed by preparingfilm-forming compositions containing the fluororesins 1 to 13 accordingto the present invention, film-forming compositions containing thecomparative fluorine-free resins 14 and 15 and film-forming compositioncontaining the PMMA, and then, applying the film-forming compositions tosilicon substrates (diameter: 10 cm, with natural oxidation films formedon respective surfaces). Each of the thus-coated substrates was immersedin the wet-etching solvent for 5 minutes. The film was evaluated ashaving resistance to the wet-etching solvent when the thickness of thefilm after the immersion was 30% or more of the thickness of the filmbefore the immersion.

For the formation of the fluororesin films on the silicon substrates,the film-forming compositions were prepared by combination of thefluororesins (concentration: 3 mass %) with a fluorine-containingsolvent and applied to the silicon substrates by spin coating; and theresulting coating films were each dried by heating on a hot plate of130° C. for 3 minutes. The fluorine-containing solvent used was a mixedsolvent of C₄F₉OCH₂CH₃, Vertrel Suprion and2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 4:4:2. Thethickness of the film was measured by an optical interference filmthickness meter (model “FTP 300” manufactured by Sentech Instruments,Germany). The concentrations of the film-forming composition and thespin coating conditions were adjusted in such a manner that thethickness of the film was in the range of 150 to 300 nm. As thewet-etching solvents, three kinds of solvents: benzene, toluene andxylene were used.

<Evaluation Results>

As a result of the evaluation test, all of the fluororesin filmscontaining the fluororesins 1 to 3 had resistance to the above threewet-etching solvents. On the other hand, the films containing thecomparative fluorine-free resins 14 and 15 and the films containing thePMMA did not have resistance to the above three wet-etching solvents.

[Evaluation Test on Insulating Property of Films]

<Evaluation Method>

The fluororesins 1 to 13 were tested for the electrical insulatingproperty. More specifically, fluororesin films containing thefluororesins 1 to 13 were formed on metal substrates (diameter: 7.5 cm,material: SUS-316) by preparing and applying film-forming compositionsaccording to the present invention. Then, gold electrodes (circularshape, diameter: 4 cm) were formed by sputtering on the fluororesinfilms. With the application of a voltage between the substrate and theelectrode, the occurrence of breakdown in the fluororesin film wasexamined.

For the formation of the fluororesin films on the metal substrates, thefilm-forming compositions were prepared by combination of thefluororesins 1 to 13 (concentration: 3 mass %) with afluorine-containing solvent and applied to the metal substrates by spincoating; and the resulting coating films were each dried by heating on ahot plate of 130° C. for 3 minutes. The fluorine-containing solvent usedwas a mixed solvent of C₄F₉OCH₂CH₃, Vertrel Suprion and2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 4:4:2. Theconcentration of the film-forming composition and the spin coatingconditions were adjusted in such a manner that the thickness of the filmwas in the range of 150 to 300 nm. The test voltage was set to 1.5 kV/mmbased on the thickness of the fluororesin film.

<Evaluation Results>

As a result of the evaluation test, there was seen no breakdown in anyof the fluororesin films with the application of the test voltage. Allof the fluororesins thus had an electrical insulating property.

[Evaluation Test on Application Property of Film-Forming Compositions toOrganic Semiconductor Films]

<Evaluation Method>

The fluororesins 1 to 13 were tested for the application property toorganic semiconductor films by the following procedure. As shown in FIG.1, an organic semiconductor film 2 was formed on a silicon substrate of10 cm diameter. A fluororesin film 3 was formed from a film-formingcomposition according to the present invention on the organicsemiconductor film 2. After that, a cross section of the thus-obtainedsubstrate was observed by an optical microscope. When there was seenlayer lamination of the organic semiconductor film 2 and the fluororesinfilm 3, the fluororesin was evaluated as having good applicationproperty and being properly applicable to the organic semiconductorfilm. The material of the organic semiconductor film herein used wasanthracene as an example of low-molecular polycyclic aromatichydrocarbon soluble in an aromatic hydrocarbon solvent.

More specifically, an anthracene film was formed with a thickness of 100nm as the organic semiconductor film 2 by preparing a solution of 0.10mass % anthracene in toluene, casting the prepared solution on thesilicon substrate and drying the casted coating at room temperature. Forthe formation of the fluororesin film 3, each of the fluororesins 1 to 4was added at a concentration of 3 mass % to a mixed solvent of Novec7300 and 2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of 7:3; andthe resulting film-forming composition was applied by spin coating tothe anthracene film-coated substrate and dried at room temperature for10 minutes.

<Evaluation Results>

As a result of the evaluation test, the anthracene film 2 and thefluororesin film 3 were laminated in layers in each example. All of thefilm-forming compositions containing the fluororesins 1 to 13 were thusapplicable on the organic semiconductor films.

[Evaluation Test on Protection of Organic Semiconductor Films byFluororesin Films]

<Evaluation Method>

Fluororesin films 3 formed from the fluororesins 1 to 13 were tested forthe ability to be removed from organic semiconductor anthracene films 2.The material of the organic semiconductor film 2 used was anthracene asan example of low-molecular polycyclic aromatic hydrocarbon soluble inan aromatic hydrocarbon solvent.

More specifically, the anthracene film 2 was formed on a siliconsubstrate. The silicon substrate used was the same as above. Thefluororesin film 3 was formed from the film-forming composition on theorganic semiconductor film 2. Then, the substrate on which theanthracene film 2 and the fluororesin film 3 were laminated in layerswas immersed in toluene for 30 seconds and subsequently immersed for 60seconds in a fluorine-containing solvent for dissolution and removal ofthe fluororesin film 3. The fluororesin film 3 was evaluated as beingable to protect the anthracene film 2 and being removable withoutaffecting the organic semiconductor film 2 when the anthracene film 2was present on the silicon substrate and did not show a thickness changeof 10% or more after the dissolution and removal of the fluororesin film3 by the fluorine-containing solvent.

For the formation of the fluororesin film 3, each of the fluororesins 1to 13 was added at a concentration of 3 mass % to a mixed solvent ofNovec 7300 and 2,2,3,3,4,4,5,5-octafluoropentanol in a mass ratio of7:3; and the resulting film-forming composition was applied by spincoating to the anthracene film-coated substrate and dried at roomtemperature for 10 minutes.

<Evaluation Results>

A thickness change of 10% or more did not occur in any of the anthracenefilms 2 when the fluororesin films 3 were removed by dissolution in thefluorine-containing solvent Novec 7200 after the immersion in toluenefor 30 seconds. It was thus possible to achieve protection of theanthracene film 2 and separation of the fluororesin film 3.

DESCRIPTION OF REFERENCE NUMERALS

-   -   1: Substrate    -   2: Organic semiconductor film or anthracene film    -   3: Fluororesin film    -   2 b: Pattern

The invention claimed is:
 1. A film-forming composition for forming afluororesin film on an organic semiconductor film, comprising: afluororesin having a repeating unit of the general formula (1)

where R¹ each independently represents a hydrogen atom, a fluorine atom,a methyl group or a trifluoromethyl group; and R² each independentlyrepresents a C₁-C₁₅ straight, C₃-C₁₅ branched or C₃-C₁₅ cyclicfluorine-containing hydrocarbon group in which any hydrogen atom may bereplaced by a fluorine atom with the proviso that the repeating unitcontains at least one fluorine atom; and a fluorine-containing solvent,wherein the fluorine-containing solvent includes either afluorine-containing hydrocarbon or a fluorine-containing ether; whereinthe fluorine-containing hydrocarbon is a C₄-C₈ straight, branched orcyclic hydrocarbon in which at least one hydrogen atom is replaced by afluorine atom; and wherein the fluorine-containing ether is afluorine-containing ether of the general formula (2)R³—O—R⁴  (2) where R³ and R⁴ each independently represent a C₁-C₁₅straight, C₃-C₁₅ branched or C₃-C₁₅ cyclic hydrocarbon group; and atleast one hydrogen atom of the ether is replaced by a fluorine atom. 2.The film-forming composition according to claim 1, wherein thefluorine-containing solvent further includes a fluorine-containingalcohol of the general formula (3)R⁵—OH  (3) where R⁵ represents a C₁-C₁₅ straight, C₃-C₁₅ branched orC₃-C₁₅ cyclic hydrocarbon group in which at least one hydrogen atom isreplaced by a fluorine atom.
 3. The film-forming composition accordingto claim 1, wherein the fluororesin has a fluorine content of 30 to 65mass %.
 4. The film-forming composition according to claim 1, whereinthe fluorine-containing solvent has a fluorine content of 50 to 70 mass%.
 5. A fluororesin film formed by applying the film-forming compositionaccording to claim 1 onto an organic semiconductor film.
 6. Amanufacturing method of an organic semiconductor element, comprising:applying the film-forming composition according to claim 1 onto anorganic semiconductor film, thereby forming a fluororesin film;patterning the fluororesin film; and etching the organic semiconductorfilm into a pattern.
 7. The manufacturing method according to claim 6,wherein the patterning of the fluororesin film is performed by aphotolithography process.
 8. The manufacturing method according to claim6, wherein the patterning of the fluororesin film is performed by aprint process.
 9. The manufacturing method according to claim 6, whereinthe patterning of the fluororesin film is performed by an imprintprocess.
 10. The manufacturing method according to claim 6, wherein theetching of the organic semiconductor film is performed by a wet etchingprocess using an aromatic solvent.
 11. The manufacturing methodaccording to claim 10, wherein the aromatic solvent is benzene, tolueneor xylene.
 12. The manufacturing method according to claim 6, furthercomprising: removing the fluororesin film.
 13. The manufacturing methodaccording to claim 12, wherein the removing of the fluororesin film isperformed by dissolving the fluororesin film in a fluorine-containingsolvent.
 14. The manufacturing method according to claim 6, wherein thefluorine-containing solvent further includes a fluorine-containingalcohol of the general formula (3)R⁵—OH  (3) where R⁵ represents a C₁-C₁₅ straight, C₃-C₁₅ branched orC₃-C₁₅ cyclic hydrocarbon group in which at least one hydrogen atom isreplaced by a fluorine atom.
 15. An organic semiconductor elementmanufactured by the manufacturing method according to claim
 6. 16. Anorganic electroluminescence display comprising the organic semiconductorelement according to claim
 15. 17. A liquid crystal display comprisingthe organic semiconductor element according to claim 15.